Metal salts of mixed dithiocarbamic acids

ABSTRACT

This invention is concerned with metal salts of mixed dithiocarbamic acids, the process for their preparation and their biological activity. In particular, these salts are useful as broad spectrum fungicidal agents.

SUMMARY OF THE INVENTION

This application is a continuation-in-part of copending U.S. Ser. No.527,794, filed Nov. 27, 1974 now abandoned.

This invention relates to metal salts of mixed dithiocarbamic acids andtheir use as broad spectrum fungicidal agents. In particular these metalsalts of mixed dithiocarbamic acids are effective in controllingBotrytis cinerea. This is particularly significant sincealkylene-bis-dithiocarbamates are ineffective against Botrytis cinerea.

The metal salts of mixed dithiocarbamic acids of this invention areprepared by the following process. Aqueous or alcoholic solutions of thesoluble alkali metal or ammonium salts of the following compounds areprepared:

(1) An alkylene-bis-dithiocarbamate of the general formula ##STR1##wherein A is a phenylene group or an alkylene chain of 2 to 6 carbonatoms which may be branched or straight chained.

(2) An alkyl or dialkyldithiocarbamate of the formula ##STR2## wherein Ris independently selected from the group consisting of hydrogen andlower alkyl of from 1 to 4 carbon atoms.

(3) An amine of the general formula ##STR3## or an ammonium orphosphonium salt the cation of which has the general formula ##STR4##wherein R¹, R², R³ and R⁴ are independently selected from the groupconsisting of hydrogen, (C₁ -C₂₀) alkyl, (C₆ -C₁₀) aryl, (C₇ -C₁₂)aralkyl, (C₁ -C₂₀) hydroxyalkyl and (C₁ -C₂₀) haloalkyl and R¹ and R²can be taken together to form a cyclic or heterogroup of the formula:##STR5## wherein Z can be a methylene group, an oxygen atom or anitrogen atom and n and m can be independently an integer from 1 to 4.These solutions are mixed together in the following molar ratios:

(1) 1.0 mole of Formula (I) to

(2) about 0.1 to 10 moles of Formula (II) to

(3) about 0.1 to 6 moles of Formula (III), (IV) or (V).

To this vigorously stirred solution is added dropwise at from about 20°C. to about 80° C. an aqueous or alcoholic solution of from about 0.75to about 6 moles of a polyvalent metal salt. A preferred molar ratio ofthis invention is 1.0 mole of Formula (I): to about 2.0 mole of Formula(II): to about 4.0 mole of Formula (III), (IV), or (V): and about 2.0mole of a polyvalent metal salt. The solvents that can be utilized inthis invention include water, methanol, ethanol, propanol, propyleneglycol and the like, preferably water. The solutions of the reagentsused in this invention are preferably at or near their saturation pointbut any concentration may be utilized.

The term "alkyl" as employed in the preceding preparation of the metalsalts of this invention is intended to indicate an alkyl group of from 1to 20 carbon atoms preferably from C₁ to C₁₀ which may be branched,straight chained or cyclized. The term "aryl" as employed in thepreceding preparation of the metal salts of this invention is intendedto indicate a phenyl or naphthyl group or a substituted phenyl ornaphthyl group which may be substituted with from one to threesubstituents selected from the group consisting of methyl, ethyl,methoxy, ethoxy, fluoro, chloro, bromo, iodo, nitro, trihalomethyl andthe like. The term "aralkyl" as employed in the preceding preparation ofthe metal salts of this invention is intended to indicate a benzyl groupor a phenethyl group or a substituted benzyl or phenethyl group whichmay be substituted with from one to three substituents selected from thegroup consisting of methyl, ethyl, methoxy, ethoxy, fluoro, chloro,bromo, iodo, nitro, trihalomethyl and the like. The term "hydroxyalkyl"as employed in the preceding preparation of the metal salts of thisinvention is intended to indicate a hydroxyalkyl group of from 1 to 20carbon atoms preferably from C₁ to C₁₀ which may be branched, straightchained or cyclized and may have up to 3 hydroxy groups. The term"haloalkyl" as employed in the preceding preparation of the metal saltsof this invention is intended to indicate a haloalkyl group of from 1 to20 carbon atoms preferably from C₁ to C₁₀ which may be branched straightchained or cyclized and may have up to 3 halo groups.

Typical compounds which are encompassed by the present inventioninclude:

Methylammonium magnesium ethylene-bis-dithiocarbamicacid-methyldithiocarbamic acid

tetraethylphosphonium calcium propylene-bis-dithiocarbamicacid-ethyldithiocarbamic acid

Tripropylammonium barium butylene-bis-dithiocarbamic acid-propyldithiocarbamic acid

tetra-(n-butyl)phosphonium aluminum pentylene-bis-dithiocarbamicacid-n-butyldithiocarbamic acid

sec-nonylammonium lead hexylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetra-(4-dodecyl)phosphonium copper ethylene-bis-dithiocarbamicacid-diethyldithiocarbamic acid

tri(7-eicosyl)ammonium zinc isopropylene-bis-dithiocarbamicacid-isopropyldithiocarbamic acid

triphenylphosphonium cadmium sec-butylene-bis-dithiocarbamicacid-sec-butyldithiocarbamic acid

di-(o,p-diethylphenyl)ammonium chromium sec-pentylene-bis-dithiocarbamicacid-dipropyldithiocarbamic acid

3,4-dihydro-1,3-oxazetidinium manganese sec-hexylene-bis-dithiocarbamicacid-di(n-butyl)dithiocarbamic acid

hexahydro-1,3-oxazocinium cobalt-phenylene-bis-dithiocarbamicacid-diisobutyldithiocarbamic acid

decahydroazecinium nickel phenylene-bis-dithiocarbamicacid-di(t-butyl)dithiocarbamic acid

3,5-dimethoxynaphthylammonium copper isopropylene bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetra-(2,4,6-trihydroxyheptyl)ammonium manganeseisobutylene-bis-dithiocarbamic acid-dimethyldithiocarbamic acid

tetrachloromethylphosphonium aluminum phenylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetra-1-fluoroethylphosphonium chromiumphenylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetra-1-bromodecylphosphonium magnesium pentylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetra-(t-butylphenyl)phosphonium zinc hexylene-bis-dithiocarbamicacid-diethyldithiocarbamic acid

tetra-(2-chloro-4-nitrophenyl)ammonium zinc propylene-bis-dithiocarbamicacid-dipropyldithiocarbamic acid

tetra-(2-methoxy-3-methylphenyl)phosphonium copperethylene-bis-dithiocarbamic acid-diethyldithiocarbamic acid

tetra-(2-nitro-4-trifluoromethylphenyl)phosphonium manganeseethylene-bis-dithiocarbamic acid-dimethyldithiocarbamic acid

tetra-(3-methyl-5-cyanobenzyl)phosphonium cobaltpropylene-bis-dithiocarbamic acid-dipropyldithiocarbamic acid

di-(3,5-dimethylphenethyl)ammonium chromiumn-butylene-bis-dithiocarbamic acid-diisobutyldithiocarbamic acid

tetra-(2-bromo-4-chlorophenyl)phosphonium nickelpropylene-bis-dithiocarbamic acid-dimethyldithiocarbamic acid

methylethylpropylammonium zinc ethylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

tetramethylphosphonium zinc ethylene-bis-dithiocarbamicacid-diethyldithiocarbamic acid

di-(2,4,5-trichlorophenyl)phosphonium zinc propylene-bis-dithiocarbamicacid-diethyldithiocarbamic acid

tetra-(2-chloro-3,5-dimethylphenyl)phosphonium copperethylene-bis-dithiocarbamic acid-dipropyldithiocarbamic acid

tetra-(2-methyl-3,5-dichlorophenyl)phosphonium manganeseethylene-bis-dithiocarbamic acid-dimethyldithiocarbamic acid

3,4,5-trimethoxy phenyl ammonium magnesium propylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

2,3,4-trimethylphenyl ammonium zinc ethylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

2,4,6-tri-t-butylphenyl ammonium zinc ethylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

It is believed that the metal salts of mixed dithiocarbamic acidsprepared by this process apparently combine in the followingstoichiometric ratio: ##STR6## wherein A and R are as defined above; Mis a metal cation selected from Groups IIA, IIIA, IVA, IB, IIB, VIB,VIIB, and VIII of the Periodic Table; Y is a group as defined by eitherFormula (III), (IV), or (V); a, b, x and y are integers and X can bezero or an integer.

When Y is a group defined by Formula (III), a is an integer which isequal to x + y/2 and b is equal to 1 or 2. When Y is a group defined byFormula (IV) or (V) a, b, x and y are integers which have therelationship that 2a + b is equal to 2x + y.

A preferred embodiment of this invention is the metal salt of mixeddithiocarbamic acids formed by mixing aqueous solutions of one mole ofan alkali metal salt of alkylene-bis-dithiocarbamate to about two molesof an alkali metal salt of alkyl or dialkyldithiocarbamate and at leastabout two moles preferably about four moles of a group of Formula (III),(IV), or (V) wherein R¹, R², R³ and R⁴ are as defined above; then addingdropwise to this mixture, at from about 25° C. to 40° C. with vigorousstirring, an aqueous solution of about two moles of a metal salt,filtering the resultant precipitate, washing it with water and drying itat 40° C. to a constant weight.

Another preferred embodiment of this invention is the metal salt ofmixed dithiocarbamic acids formed by simultaneously adding aqueoussolutions of (a) one mole of an alkali metal salt ofalkylenebisdithiocarbamate and about two moles of an alkali metal saltof alkyl or dialkyldithiocarbamate and (b) an aqueous solution of abouttwo moles of a metal salt to an aqueous solution of about four moles ofa group of Formula (III), (IV) or (V) wherein R¹, R², R³ and R⁴ are asdefined above, at temperatures of from about 25° C. to about 40° C. withvigorous stirring. The resultant precipitate is filtered washed withwater and dried at 40° C. to a constant weight.

Another preferred embodiment of this invention is the metal salt ofmixed dithiocarbamic acids formed by mixing an aqueous solution of onemole of an alkali metal salt of alkylene-bis-dithiocarbamate, about twomoles of an alkali metal salt of alkyl or dialkyldithiocarbamate andabout four moles of a group of Formula (III), (IV) or (V), wherein R¹,R², R³ and R⁴ are as defined above, simultaneously with an aqueoussolution of about two moles of a metal salt, the point of mixing takingplace in a vigorously stirred vessel which may or may not contain water,at temperatures of from about 25° C. to about 40° C.

In the more preferred embodiment of this invention, the metal saltswhich can be utilized can be selected from any of the followingcombinations of metal ions such as Mg, Ca, Ba, Al, Pb, Cu, Zn, Cd, Cr,Mn, Co, and Ni and any of the following anion counterions such aschloride, bromide, iodide, sulfate, bisulfate, phosphate, nitrate,perchlorate, carbonate, bicarbonate, hydrosulfide, hydroxide, acetate,oxalate, malate, nitrate or tartarate; the most preferred salt beingzinc chloride.

The most preferred alkylene-bis-dithiocarbamate which can be utilized inthe above procedure is ethylene-bis-dithiocarbamate and the mostpreferred dialkyldithiocarbamate is dimethyl dithiocarbamate.

The following examples are provided merely to facilitate one skilled inthe art to better understand how to prepare exemplary complex metalsalts of this invention. It is understood, however, that these examplesare intended for illustration only and it is not intended that theinvention be limited thereby.

EXAMPLE 23 Trimethylammonium Manganese Ethylene-bis-dithiocarbamicacid-Dimethyldithiocarbamic acid

A 100 ml. aqueous solution of 8.44g. (0.05 mole) of manganese sulfatemonohydrate is added dropwise to a 3-necked flask. After 5-10 ml. of thesolution has been added, a combined 100 ml. aqueous solution of 6.6g. ofsodium ethylene-bis-dithiocarbamate (0.025 mole), 8.95g. of sodiumdimethyldithiocarbamate (0.05 mole) and 9.5g. (0.1 mole) oftrimethylamine hydrochloride is added simultaneously to the flask at thesame rate as that of the metal salt solution. After the addition (ca 15min.) the suspension is stirred for 0.5 hour then vacuum filtered,reslurried with water, and filtered again. The collected precipate isair-dried overnight then vacuum dried until it reaches a constantweight. A total of 13.7g. of product, mp>250° C. (dec) is obtained.

EXAMPLE 50 Preparation of Tetramethylammonium ZincEthylene-bis-dithiocarbamic acid-Dimethyldithiocarbamic acid

Aqueous solutions (20%) of disodium ethylene-bis-dithiocarbamate(6.85g., 0.025 mole), dimethyldithiocarbamic acid sodium saltdihydrate(9.0g., 0.05 mole), and tetramethyl ammonium bromide (15.4g.,0.1 mole) are prepared separately. The above solutions are then mixed tothis mixture is added an aqueous solution (20%) of zinc chloride(6.96g., 0.05 mole) dropwise with rapid stirring. The reaction mixtureis stirred for 10 more minutes. The precipitate formed is collected byfiltration and washed with water. It is dried in a vacuum oven at 40°until it gives a constant weight. A total of 15.7g. of product, mp.134°-6° C. is obtained.

EXAMPLE 51 Preparation of Ammoniated Zinc Ethylene-bis-dithiocarbamicacid-Dimethyldithiocarbamic acid

Aqueous solutions (20%) of disodium ethylene-bis-dithiocarbamate(6.85g., 0.025 mole) and dimethyldithiocarbamic acid sodium saltdihydrate (9.0g., 0.05 mole) are prepared separately and then mixedtogether. To this mixture is added 6.75 ml. (0.1 mole) of concentratedammonium hydroxide followed by addition dropwise of an aqueous solution(20%) of zinc chloride (6.96g., 0.05 mole) with rapid stirring. Thereaction mixture is stirred for 10 more minutes. The precipitate formedis collected by filtration and washed with water. It is dried in avacuum oven at 40° C. until it gives a constant weight. A total of 14g.,of product, mp. 142°-5° C. is obtained.

EXAMPLE 52 Preparation of Dimethylammonium ZincEthylene-bis-dithiocarbamic acid-Dimethyldithiocarbamic acid

Aqueous solutions (20%) of disodium ethylene-bis-dithiocarbamate(6.85g., 0.025 mole), dimethyldithiocarbamic acid sodium salt dihydrate(9.0g., 0.05 mole), and dimethylamine hydrochloride (8.2g., 0.1 mole)are prepared separately. To a mixture of the above solutions is added anaqueous solution (20%) of zinc chloride (6.96g., 0.05 mole) dropwisewith rapid stirring. The reaction mixture is stirred for 10 moreminutes. The precipitate formed is collected by filtration and washedwith water. It is then dried in a vacuum oven at 40° C. until it gives aconstant weight. A total of 14.2g. of product, mp. 137°-41° C. isobtained.

EXAMPLE 53 Trimethyl(2-hydroxyethyl)ammonium ZincEthylene-bis-dithiocarbamic acid-Dimethyldithiocarbamic acid

A 100 ml. aqueous solution of 6.95g. (0.05 mole) of zinc chloride isadded dropwise to a 3-necked flask containing 50 ml. of water. After5-10 ml. of the solution has been added, a combined 100 ml. aqueoussolution of 6.5g. (0.025 mole) of sodium ethylene-bis-dithiocarbamate,8.95g. (0.05 mole) of sodium dimethyldithiocarbamate and 13.6g. (0.1mole) of trimethyl(2-hydroxyethyl)ammonium chloride (choline chloride)is added to the flask at the same rate as that of the metal saltsolution. After the addition, the suspension is stirred 0.5 hour thenfiltered under vacuum, reslurried with water, and filtered again. Thecollected precipitate is air-dried overnight then dried under vacuumuntil it reaches a constant weight. A total of 15.3g. of product, mp120°-124° C. is obtained.

EXAMPLE 54 Tetramethylammonium Zinc Ethylene-bis-dithiocarbamicacid-Dimethyldithiocarbamic acid

To a well stirred aqueous solution of 6.85g. (0.027 mole) of sodiumethylene-bis-dithiocarbamate, 9.0g., (0.05 mole) of sodiumdimethyldithiocarbamate and 10.9g. (0.1 mole) of tetramethylammoniumchloride is added dropwise at room temperature 6.96g. (0.05 mole) ofzinc chloride dissolved in 30 ml. of water. A very fine dispersed whiteprecipitate forms immediately. The reaction mixture is stirred for anadditional ten minutes then filtered under vacuum. The collected solidis transferred to a beaker, reslurried with water, then filtered again.The white solid is air-dried for two days then dried under vacuum at 45°C. until it reaches a constant weight. A total of 15.2g. of products mp.128°-132° C. is obtained.

EXAMPLE 55 Trimethylammonium Zinc Ethylene-bis-dithiocarbamicacid-Dimethyldithiocarbamic acid

A 100 ml. aqueous solution of 6.95g. (0.05 mole) of zinc chloride isadded dropwise to a 3-necked flask containing 50 ml. of water. After5-10 ml. of the solution has been added, a combined 100 ml. aqueoussolution of 6.5g. (0.025 mole) of sodium ethylene-bis-dithiocarbamate,8.95g. (0.05 mole) of sodium dimethyldithiocarbamate and 9.6g. (0.1mole) of trimethylamine hydrochloride is added to the flask at the samerate as that of the metal salt solution. After the addition, thesuspension is stirred 0.5 hour then filtered under vacuum, reslurriedwith water and filtered again. The collected precipitate is air-driedovernight then dried under vacuum at 45° until it reaches a constantweight. A total of 14.6g. of product, mp 134°-137° C is obtained.

EXAMPLE 57 Trimethylammonium Manganese-Zinc Ethylene-bis-dithiocarbamicacid-Dimethyldithiocarbamic acid

A 100 ml. aqueous solution of 8.44g. (0.05 mole) of manganese sulfatemonohydrate is added dropwise to a 3-necked flask. After 5-10 ml. of thesolution had been added, a combined 100 ml. solution of 6.5g. of sodiumethylene-bis-dithiocarbamate (0.025 mole), 8.95g. of sodiumdimethyldithiocarbamate (0.05 mole) and 9.5g. (0.1 mole) oftrimethylamine hydrochloride is added simultaneously to the flask at thesame rate as that of the manganese solution. After the addition (ca 15min.) the suspension is stirred for 0.5 hour then vacuum filtered. Theprecipitate is added to a beaker containing 100 ml. of water and asolution of ZnCl₂ (0.005 mole) is added with efficient stirring. Thesuspension is refiltered and the precipitate is air-dried for six hoursthen vacuum dried until it reaches a constant weight. A total of 14.4g.of product, mp>˜250° C. (dec.) is obtained.

EXAMPLE 75 Dimethylammonium Manganese Piperazine dithiocarbamicacid-Dodecyldithiocarbamic acid

Sodium hydroxide 4.0g. (0.1 mole) is added to a 3-necked flaskcontaining an addition funnel, a mechanical stirrer, and a refluxcondenser. Water (25 ml.) is added and the solution is stirred at roomtemperature while 2.15g. (0.025 mole) of piperazine and 9.25g. (0.05mole) of dodecylamine is added. Carbon disulfide 7.6g (0.1 mole) is thenadded at such a rate so as to keep the flask temperature below 46° C.The orange solution is stirred for 2.5 hours after which time 8.15g.(0.1 mole) of dimethylamine hydrochloride is added followed by asolution of 9.9g. (0.05 mole) of MnCl₂.4H₂ O. The suspension is stirredan additional 0.5 hour then vacuum filtered, reslurried, andre-filtered. The collected precipitate is air-dried overnight thenvacuum dried until it reaches a constant weight. A total of 20.7g. ofproduct mp. 200° C. (dec.) is obtained.

EXAMPLE 85 Preparation of N,N-Dimethylethanolammonium Zinc Ethylene-bisdithiocarbamic acid-Dimethyldithiocarbamic acid

Aqueous solutions (20%) of disodium ethylene-bis-dithiocarbamate(6.85g., 0.025 mole), dimethyldithiocarbamic acid sodium salt dihydrate(9.0g., 0.05 mole), and N,N-dimethylethanol amine (8.9g., 0.1 mole) areprepared separately. The above solutions are then mixed and to thismixture is added an aqueous solution (20%) of zinc chloride (6.96g.,0.05 mole) dropwise with rapid stirring. The reaction mixture is stirredfor 10 more minutes. The precipitate formed is collected by filtrationand washed with water. It is dried in a vacuum oven at 40° C. until itgives a constant weight. A total of 12.5g. of product, mp. 211°-214° C.is obtained.

EXAMPLE 86 (n-Butyl)-triphenylphosphonium ZincEthylene-bis-dithiocarbamic acid Dimethyldithiocarbamic acid

Ten grams (0.05 mole) of (n-butyl)-triphenylphosphonium bromide is addedto 100 ml. of water contained in a 3-necked flask. To this homogeneoussolution is slowly added a 100 ml. aqueous solution of zinc chloride6.8g. (0.05 mole). After about 10 ml. of the zinc chloride solution hasbeen added, a combined 100 ml. aqueous solution of sodiumdimethyldithiocarbamate 8.95g. (0.05 mole) is added at the same rate asthat of the metal salt solution. At the end of the addition thevoluminous precipitate that forms is collected by vacuum filtration andair-dried overnight then dried under vacuum until it reaches a constantweight. A total of 27.4g. of product mp 79°-81° C. is obtained.

EXAMPLE 87 General procedure for the preparation of trimethyl(2-hydroxyethyl) ammonium Zinc Ethylene-bis-dithiocarbamicacid-dimethyldithiocarbamic acid

A 100 ml. aqueous solution of the zinc chloride is added dropwise to a3-necked flask containing 50 ml. of water. After 5-10 ml. of thesolution has been added, a combined 100 ml. aqueous solution of sodiumethylenebisdithiocarbamate, sodium dimethyldithiocarbamate and trimethyl(2-hydroxyethyl) ammonium chloride (choline chloride) is added to theflask at the same rate as that of the metal salt solution. After theaddition, the suspension is stirred for 0.5 hour then filtered undervacuum reslurried with water, and filtered again. The collectedprecipitate is air-dried overnight then dried under vacuum until itreaches a constant weight.

Table I below gives the metal salt complexes which can be formed by theutilization of the procedures given in Examples 23, 50, 51, 52, 53, 54,55, 58, 75, 85, 86 and 87 when the following ratios of reagents areused:

(a) one mole of disodium ethylene-bis-dithiocarbamate;

(b) two moles of sodium dimethyldithiocarbamate;

(c) two moles of zinc sulfate and;

(d) four moles of a quaternary ammonium salt.

                                      TABLE I                                     __________________________________________________________________________                            Elemental Analysis - % Found                          Example No.                                                                           R.sup.1 R.sup.2 R.sup.3 R.sup.4 NX.sup.-.sup.+                                                mp° C                                                                      C   H   N   S   Zn                                __________________________________________________________________________             ##STR7##       126-9                                                                             24.90                                                                             4.37                                                                              10.47                                                                             37.12                                                                             13.10                             2       (CH.sub.3).sub.3 N . HCl                                                                      >250                                                                              22.34                                                                             3.84                                                                              10.00                                                                             3.30                                                                              17.3                              3       CH.sub.3 NH.sub.2 . HCl                                                                       141-5                                                                             21.24                                                                             3.37                                                                              10.762                                                                            41.87                                                                             19.1                              4       (CH.sub.3).sub.2 NH . HCl                                                                     138-42                                                                            22.57                                                                             3.73                                                                              10.65                                                                             43.04                                                                             19.4                              5       n-C.sub.4 H.sub.9 NH.sub.2 . HCl                                                              116-8                                                                             25.97                                                                             4.66                                                                              10.91                                                                             40.13                                                                             16.7                              6                                                                                      ##STR8##       125-8                                                                             26.32                                                                             4.34                                                                              10.41                                                                             44.42                                                                             17.9                              7                                                                                      ##STR9##       80-5                                                                              32.55                                                                             4.60                                                                              10.44                                                                             36.23                                                                             14.8                              8                                                                                      ##STR10##      109-12                                                                            25.07                                                                             4.24                                                                              10.15                                                                             32.29                                                                             18.1                              9                                                                                      ##STR11##      103-6                                                                             33.78                                                                             4.74                                                                              9.54                                                                              33.2                                                                              12.4                              10      n-C.sub.8 H.sub.17 NH.sub.2 . HCl                                                             112-6                                                                             33.93                                                                             5.84                                                                              10.60                                                                             36.42                                                                             13.1                              11      NH.sub.2 (CH.sub.2).sub.3 NH.sub.2 . 2HCl                                                     129-34                                                                            21.95                                                                             3.70                                                                              10.68                                                                             40.92                                                                             17.1                              12                                                                                     ##STR12##      73-8                                                                              51.73                                                                             8.19                                                                              6.83                                                                              23.25                                                                             9.0                               13      NH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 . 2HCl                                                    115-7                                                                             21.84                                                                             3.71                                                                              11.10                                                                             41.63                                                                             17.0                              14                                                                                     ##STR13##      128-32                                                                            24.74                                                                             4.02                                                                              10.76                                                                             40.17                                                                             16.9                              15      CH.sub.3 (CH.sub.2).sub.11 NH.sub.2 . HCl                                                     86-9                                                                              48.56                                                                             9.26                                                                              8.31                                                                              20.98                                                                             9.20                              16      HOCH.sub.2 CH.sub.2 NH.sub.2 . 1HCl                                                           124-7                                                                             21.37                                                                             3.51                                                                              10.40                                                                             39.62                                                                             18.10                             17      NH.sub.2 (CH.sub.2).sub.6 NH.sub.2 . 2HCl                                                     126-30                                                                            24.33                                                                             4.25                                                                              11.02                                                                             46.77                                                                             15.50                             18      CH.sub.3 CH(NH.sub.2)CH.sub.2 CH.sub.3 . HCl                                                  119-23                                                                            23.54                                                                             4.06                                                                              9.96                                                                              26.66                                                                             16.80                             19      CH.sub.3 (C.sub.2).sub.13 N(CH.sub.3).sub.2 . HCl                                             88-93                                                                             41.81                                                                             7.60                                                                              8.33                                                                              26.26                                                                             13.1                              __________________________________________________________________________

Table II below gives the metal salt complexes formed by the utilizationof the following reagents when the procedures of Examples 23, 50, 51,52, 53, 54, 55, 58, 75, 85, 86 and 87 are followed:

(a) one mole of disodium ethylene-bis-dithiocarbamate;

(b) two moles of sodium dimethyldithiocarbamate;

(c) two moles of manganese sulfate and;

(d) four moles of a quaternary ammonium salt.

                                      Table II                                    __________________________________________________________________________                            Elemental Analysis - % Found                          Example No.                                                                           R.sup.1 R.sup.2 R.sup.3 R.sup.4 NX.sup.-.sup.+                                                 mp° C.                                                                       C   H   N   S   Mn  O                          __________________________________________________________________________    20      n-C.sub.4 H.sub.9 NH.sub.2 . HCl                                                              230 (dec.)                                                                           22.83                                                                             3.80                                                                              9.43                                                                              39.33                                                                             16.2                                                                              9.47                       21      N-C.sub.8 H.sub.17 NH.sub.2 . HCl                                                             229-31 35.96                                                                             6.34                                                                              9.44                                                                              30.60                                                                             7.00                                                                              9.96                       22                                                                                     ##STR14##      >50    31.82                                                                             4.54                                                                              8.86                                                                              27.44                                                                             9.80                                                                              9.00                       23      (CH.sub.3).sub.3 N . HCl                                                                      >250   21.71                                                                             3.60                                                                              9.90                                                                              49.89                                                                             15.30                                                                             7.89                       24                                                                                     ##STR15##      250 (dec.)                                                                           25.44                                                                             4.10                                                                              10.19                                                                             38.33                                                                             13.40                                                                             9.13                       25      (CH.sub.3).sub.2 NH . HCl                                                                     >250   21.38                                                                             3.38                                                                              11.25                                                                             38.71                                                                             16.3                                                                              10.1+                      26      HOCH.sub.2 CH.sub.2 NH.sub.2 . HCl                                                            >250   20.04                                                                             3.25                                                                              9.32                                                                              40.63                                                                             16.0                                                                              12.61                      27      NH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 . 2HCl                                                    >250   20.21                                                                             3.35                                                                              10.25                                                                             36.88                                                                             14.3                                                                              13.33                      28      NH.sub.2 (C.sub.2).sub.6 NH.sub.2 . 2HCl                                                      >250   22.54                                                                             3.80                                                                              1.26                                                                              37.28                                                                             13.8                                                                              12.89                      29                                                                                     ##STR16##      >250   21.36                                                                             3.56                                                                              9.94                                                                              36.62                                                                             14.2                                                                              12.56                      30      HCCC(CH.sub.3).sub.2 NH.sub.2 . HCl                                                           >250   21.24                                                                             3.36                                                                              9.79                                                                              21.20                                                                             15.2                                                                              11.6+                      31                                                                                     ##STR17##      >250   22.81                                                                             3.70                                                                              9.24                                                                              32.59                                                                             15.2                                                                              9.88                       32      CH.sub.3 CH(NH.sub.2)CH.sub.2 CH.sub.3 . HCl                                                  >250/ 21.86                                                                          3.73                                                                              9.27                                                                              35.37/ 12.12                                                                      10.15                              33      (CH.sub.3).sub.3 CCH.sub.2 C(CH.sub.3).sub.2 NH.sub.2 .                                       250    25.78                                                                             4.53                                                                              9.85                                                                              34.95                                                                             12.3                                                                              8.17                       34      (HOCH.sub.2 CH.sub.2).sub.3 N . HCl                                                           >250   23.80                                                                             3.60                                                                              10.24                                                                             38.44                                                                             15.2                                                                              6.02                       35      PhCH.sub.2 NH.sub.2 . HCl                                                                     230 (dec.)                                                                           2.68                                                                              3.79                                                                              1.57                                                                              35.10                                                                             13.0                                                                              5.50                       36      NH.sub.4 OH     235    19.13                                                                             3.15                                                                              8.44                                                                              33.56                                                                             19.1                                                                              12.05                      37      t-C.sub.8 amines (mixture)                                                                    240 (dec.)                                                                           39.00                                                                             6.63                                                                              7.17                                                                              25.43                                                                             9.2 10.++                      38                                                                                     ##STR18##      115    48.98                                                                             7.60                                                                              6.52                                                                              18.70                                                                             6.4 6.77                       39      CH.sub.3 (CH.sub.2).sub.11 NHC(NH)NH.sub.2 .                                                  205 (dec.)                                                                           31.99                                                                             5.60                                                                              9.94                                                                              19.38                                                                             6.2 8.67                               CH.sub.3 COOH                                                         __________________________________________________________________________

When the procedures of Examples 23, 50, 51, 52, 53, 54, 55, 58, 75, 85,86 and 87 are followed and the following ratios of reagents are utilizedthe metal salt complexes of Table III are readily obtained:

(a) one mole of disodium ethylene-bis-dithiocarbamate

(b) two moles of sodium dimethyldithiocarbamate

(c) two moles of a metal salt and,

(d) four moles of a quaternary ammonium salt.

                                      Table III                                   __________________________________________________________________________                                     Elemental Analysis - % Found                 Example No.                                                                          Metal Salt  R.sup.1 R.sup.2 R.sup.3 R.sup.4 N.sup.+ X.sup.-                                             mp° C                                                                       C  H  N  S  Metal                                                                              O                      __________________________________________________________________________    40     MnCl.sub.2  (CH.sub.3).sub.4 N.sup.+ Br.sup.-                                                           250 (dec)                                                                          23.18                                                                            3.98                                                                              9.74                                                                            38.50                                                                            13.7/--                                                                            --                     41     NiCl.sub.2 . 6H.sub.2 O                                                                   (CH.sub.3).sub.3 N . HCl                                                                    >250 21.45                                                                            3.43                                                                             10.88                                                                            37.05                                                                            17.5/--                                                                            --                     42     FeCl.sub.3 . 6H.sub.2 O                                                                   (CH.sub.3).sub.3 N . HCl                                                                    228-32                                                                             21.92                                                                            3.35                                                                             10.88                                                                            36.85                                                                            11.40/--                                                                           5.28                   43     CoCl.sub.2  (CH.sub.3).sub.3 N . HCl                                                                    >250 21.32                                                                            3.29                                                                              9.58                                                                            35.88                                                                            13.70/--                                                                           6.09                   44     CdCl.sub.2  (CH.sub.3).sub.3 N . HCl                                                                    >250 18.79                                                                            3.06                                                                              8.51                                                                            33.94                                                                            29.0/--                                                                            3.29                   45     CuBr.sub.2  (CH.sub.3).sub.3 N . HCl                                                                    >250 19.86                                                                            3.27                                                                              9.40                                                                            30.42                                                                            19.3/--                                                                            3.24                   46     MnCl.sub.2  (CH.sub. 3).sub.3 N . HCl                                                                   >250 25.26                                                                            4.59                                                                             11.28                                                                            40.68                                                                            13.40/--                                                                           3.90                   47     CuSO.sub.4  (CH.sub.3).sub.3 NCH.sub.2 CH.sub.2 OHCl.sup.-                                              >250 22.27                                                                            4.45                                                                              9.92                                                                            35.78                                                                            18.3/--                                                                            5.12                   48     FeCl.sub.3 . 6H.sub.20                                                                    CH.sub.3 NH.sub.2 . HCl                                                                     205-210                                                                            22.25                                                                            3.22                                                                             10.76                                                                            44.88                                                                            11.1/--                                                                            5.83                   49     FeCl.sub.3 . 6H.sub.2 O                                                                   (CH.sub.3).sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHCl.sup.-                                       200  24.17                                                                            3.54                                                                             11.4                                                                             42.12                                                                            11.4/--                                                                            7.68                   50     ZnCl.sub.2  (CH.sub.3).sub.4 N.sup.+ Br.sup.-                                                           134-6                                                                              24.70                                                                            4.56                                                                             10.40                                                                            39.43                                                                            17.80/--                                                                           --                     51     ZnCl.sub.2  N.sup.+ H.sub.4 OH.sup.-                                                                    142-5                                                                              19.18                                                                            4.04                                                                             13.81                                                                            41.41                                                                            18.10/--                                                                           --                     52     ZnCl.sub.2  (CH.sub.3).sub.2 N . HCl                                                                    137-41                                                                             21.70                                                                            3.64                                                                             10.43                                                                            40.12                                                                            16.50/--                                                                           --                     53     ZnCl.sub.2  (CH.sub.3).sub.3 N.sup.+ CH.sub.2 CH.sub.2 OHCl.sup.-                                       120-4                                                                              25.60                                                                            4.51                                                                             10.49                                                                            38.14                                                                            16.80/--                                                                           8.06                   54     ZnCl.sub.2  (CH.sub.3).sub.4 N.sup.+ Cl.sup.-                                                           128-32                                                                             24.56                                                                            4.28                                                                             10.61                                                                            39.55                                                                            17.20/--                                                                           --                     55     ZnCl.sub.2  (CH.sub.3).sub.3 N . HCl                                                                    134-37                                                                             22.64                                                                            3.83                                                                             10.58                                                                            38.43                                                                            18.5/--                                                                            --                     56     CuSO.sub.4  (CH.sub.3).sub.3 N . HCl                                                                    220 (dec)                                                                          21.54                                                                            3.39                                                                              9.89                                                                            38.19                                                                            21.2/--                                                                            3.13                   57     MnSO.sub.4 . H.sub.2 O/ZnCl.sub.2                                                         (CH.sub.3).sub.3 N . HCl                                                                    250 (dec)                                                                          22.95                                                                            3.95                                                                             10.57                                                                            40.36                                                                            14.1/0.5                                                                           6.08                   58     ZnCl.sub.2 /FeCl.sub.3 . 6H.sub.2 O                                                       CH.sub.3 NH.sub.2 . HCl                                                                     140-5                                                                              20.73                                                                            3.21                                                                             10.39                                                                            42.53                                                                            18.6/0.6                                                                           3.47                   59     MnSO.sub.4 . H.sub.2 O/CuSO.sub.4                                                         CH.sub.3 NH.sub.2 . HCl                                                                     >250 18.33                                                                            3.18                                                                             8.85                                                                             34.93                                                                            13.8/2.9                                                                           14.05                  60     ZnSO.sub.4 /ZnCl.sub.2                                                                    (CH.sub.3).sub.3 N . HCl                                                                    >250 23.17                                                                            3.82                                                                             10.78                                                                            42.08                                                                            20.1/--                                                                            --                     61     ZnCl.sub.2 /FeCl.sub.3                                                                    (CH.sub.3).sub.3 N . HCl                                                                    130 (dec)                                                                          22.71                                                                            3.78                                                                             10.31                                                                            42.55                                                                            16.1/0.86                                                                          2.88                   62     MnSO.sub.4 /CuSO.sub.4                                                                    (CH.sub.3).sub.3 N . HCl                                                                    >250 19.78                                                                            3.64                                                                              9.24                                                                            35.35                                                                            12.8/3.4                                                                           13.4                   __________________________________________________________________________

In Table IV the metal salt complexes are given which are formed byfollowing the procedures of Examples 23, 50, 51, 52, 53, 54, 55, 58, 75,85, 86 and 87 and utilizing the following molar ratios of reagents:

(a) one mole of a disodium alkylene or phenylene-bis-dithiocarbamate ofthe formula R'--C(S)SNa]₂

(b) two moles of a sodium disubstituted dithiocarbamate of the formulaR" C(S)SNa

(c) two moles of a metal salt and,

(d) four moles of either dimethylamine hydrochloride or trimethylaminehydrochloride *

                                      Table IV                                    __________________________________________________________________________                                          Elemental Analysis - % Found            Example No.                                                                          Metal Salt                                                                           R             R"        mp` C.                                                                              C  H  N  S  Metal                                                                             O                 __________________________________________________________________________    64     MnSO.sub.4                                                                           NH(CH.sub.2).sub.6 NH                                                                        ##STR19##                                                                              155 (dec)                                                                           36.59                                                                            4.86                                                                             10.41                                                                            30.71                                                                            9.7 6.93              65     MnSO.sub.4                                                                           NH(CH.sub.2).sub.6 NH                                                                       (CH.sub.3).sub.2 N                                                                      170 (dec)                                                                           24.46                                                                            4.05                                                                             8.69                                                                             34.23                                                                            13.0                                                                              8.87              66     MnSO.sub.4                                                                           NH(CH.sub.2).sub.6 NH                                                                       CH.sub.3 NH                                                                             180 (dec)                                                                           26.21                                                                            3.65                                                                             9.06                                                                             43.64                                                                            26.9                                                                              14.74             67     MnSO.sub.4                                                                           NHCH.sub.2 CH(CH.sub.3)NH                                                                   (CH.sub.3).sub.2 N                                                                      >250  20.88                                                                            3.51                                                                             9.21                                                                             35.95                                                                            19.8                                                                              9.33              68     MnSO.sub.4                                                                           NH(CH.sub.2).sub.3 NH                                                                       (CH.sub.3).sub.2 N                                                                      >250  20.28                                                                            3.41                                                                             8.62                                                                             36.11                                                                            20.7                                                                              8.01              69     MnSO.sub.4                                                                           NH(CH.sub.2).sub.2 NH                                                                       CH.sub.3 NH                                                                             235 (dec)                                                                           17.78                                                                            3.44                                                                             10.60                                                                            36.42                                                                            12.0                                                                              16.03             70     MnSO.sub.4                                                                           NH(CH.sub.2).sub.3 NH                                                                       CH.sub.3 NH                                                                             250 (dec)                                                                           20.14                                                                            3.28                                                                             9.90                                                                             38.26                                                                            15.0                                                                              11.22             71     MnSO.sub.4                                                                           NH(CH.sub.2).sub.3 NH                                                                       PhCH.sub.2 NH                                                                           215   35.56                                                                            3.85                                                                             9.83                                                                             29.32                                                                            10.5                                                                              8.32              72     MnSO.sub.4                                                                           NH(CH.sub.2).sub.4 NH                                                                       CH.sub.3 NH                                                                             250   20.85                                                                            3.25                                                                             9.43                                                                             35.24                                                                            16.1                                                                              11.95             73     MnSO.sub.4                                                                           NH(CH.sub.2).sub.4 NH                                                                       (CH.sub.3).sub.2 N                                                                      250   23.54                                                                            3.89                                                                             10.66                                                                            36.24                                                                            13.4                                                                              7.88              74     MnSO.sub.4                                                                           NH(CH.sub.2).sub.4 NH                                                                       CH.sub.3 (CH.sub.2).sub.11 NH                                                           120   48.66                                                                            8.11                                                                             5.75                                                                             12.22                                                                            18.4                                                                              7.87              75     MnSO.sub.4                                                                            ##STR20##    CH(CH.sub.2).sub.11 NH                                                                  200 (dec)                                                                           44.29                                                                            6.89                                                                             7.42                                                                             18.57                                                                            13.1                                                                              7.36              76     MnSO.sub.4                                                                            ##STR21##    CH.sub.3 (CH.sub.2).sub.11 NH                                                           230 (dec)                                                                           48.99                                                                            6.88                                                                             8.00                                                                             23.18                                                                            8.3 5.95              77     MnSO.sub.4                                                                           NH(CH.sub.2).sub.3 NH                                                                       NH.sub.2  220 (dec)                                                                           22.18                                                                            3.21                                                                             11.24                                                                            34.17                                                                            15.3                                                                              11.83              78*   FeCl.sub.3                                                                           NH(CH.sub.2).sub.2 NH                                                                       CH.sub.3 NH                                                                             >250  13.35                                                                            2.14                                                                             7.49                                                                             44.74                                                                            19.6                                                                              10.97              79*   ZnCl.sub.2                                                                           NH(CH.sub.2).sub.2 NH                                                                       CH.sub.3 NH                                                                             108- 12                                                                             20.76                                                                            3.93                                                                             11.45                                                                            46.99                                                                            20.3                                                                              1.98               80*   MnSO.sub.4                                                                           NH(CH.sub.2).sub.2 NH                                                                       CH.sub.3 NH                                                                             >250  15.31                                                                            2.59                                                                             9.28                                                                             36.70                                                                            19.4                                                                              17.6               81*   CuSO.sub.4                                                                           NH(CH.sub.2).sub.2 NH                                                                       CH.sub.3 NH                                                                             >250  17.09                                                                            2.89                                                                             9.26                                                                             37.66                                                                            25.5                                                                              --                __________________________________________________________________________

Table V gives the metal salt complexes formed by following theprocedures of Examples 23, 50, 51, 52, 53, 54, 55, 58, 75, 85, 86 and 87when the following molar ratios are utilized:

(a) one mole of disodium ethylene-bis-dithiocarbamate;

(b) two moles of sodium dimethyl dithiocarbamate;

(c) two moles of zinc chloride and;

(d) four moles of amine as the free base.

                                      Table V                                     __________________________________________________________________________                             Elemental Analysis - % Found                         Example No.                                                                           R.sup.1 R.sup.2 R.sup.3 N                                                                 mp° C                                                                       C  H  N  S  Metal                                                                             O                                    __________________________________________________________________________    82      (HOCH.sub.2 CH.sub.2).sub.3 N                                                             144-50                                                                             22.45                                                                            3.82                                                                             9.75                                                                             39.59                                                                            20.6                                                                              3.32                                 83      (CH.sub.3 CH.sub.2).sub.2 NH                                                              200-8                                                                              19.82                                                                            3.39                                                                             8.21                                                                             35.83                                                                            25.9                                                                              5.70                                 84      CH.sub.3 NH.sub.2                                                                         133-6                                                                              20.11                                                                            3.34                                                                             10.15                                                                            39.47                                                                            22.9                                                                              3.68                                 85      (CH.sub.3).sub.2 NCH.sub.2 CH.sub.2 OH                                                    211-4                                                                              20.30                                                                            3.57                                                                             8.51                                                                             34.30                                                                            24.7                                                                              5.22                                 __________________________________________________________________________

Table VI gives the metal salt complexes formed by following theprocedure of Example 87 and utilizing the indicated molar ratios.

                  Table VI                                                        ______________________________________                                             Zinc     HOCH.sub.2 CH.sub.2 N.sup.+                                     Ex.  Chloride (CH.sub.3).sub.3 Cl.sup.-                                                                  EBDC  DMDC                                         No.  (moles)  (moles)      (moles)                                                                             (moles)                                                                              mp° C                          ______________________________________                                        88   (1.0)    (0.1)        (1.0) (0.1)  144 (dec)                             89   (0.75)   (0.5)        (1.0) (0.1)  134-6                                 90   (1.2)    (2.0)        (1.0) (1.0)  124-6                                 91   (6.0)    (3.0)        (1.0) (10.0) 170 (dec)                             92   (1.6)    (0.85)       (1.0) (2.0)  175-80                                ______________________________________                                    

The mixed dithiocarbamic acid metal salts of this invention exhibitbroad spectrum fungicidal activity when used as a topical fungicide andis especially effective for the foliar control of tomato late blight(Phytophtora infestans) on tomato seedlings, grape downy mildew(Plasmopora viticola) on grape seedlings, wheat stem rust (Pucciniagraminis f. sp. tritici) on wheat plants, rice blast (Piriculariaoryzae) on rice plants and barley net blotch (Helminthosporium teres) onbarley plants.

In particular the salts of this invention show control of Botrytiscinerea on broad beans (Vicia faba). This is particularly importantsince (mancozeb) the zinc complex of maganeseethylene-bis-dithiocarbamate shows no activity against Botrytis cinerea.

The salts of this invention exhibit an unexpected activity againstBotrytis cinerea on broad beans (Vicia faba), an activity which isnon-existent with ethylene-bis-dithiocarbamates. In this test broadbeans are trimmed to a height of approximately 4.5 inches 24 hours priorto chemical application, the plants are sprayed to runoff with thechemical agent and allowed to dry. The plants are inoculated withBotrytis cinerea and incubated in a humid environment at 75°-80° F for66 hours. The plants lesions are evaluated 66 to 68 hours afterinoculation.

The control of bean powdery mildew (Erysiphe polygoni) is demonstratedby the following procedure. Bean plants (var. Dwarf Hort) are thinned totwo plants per pot 24 hours prior to chemical application. The plantsare sprayed to runoff with the chemical agent and allowed to dry. Theplants are then inoculated with Erysiphe polygoni and maintained underexisting greenhouse conditions. Treatment comparisions are made 8 to 10days after inoculation.

The salts of this invention are effective in controlling tomato lateblight (Phytophtora infestans) on tomato seedlings. In this test, theplants are sprayed to runoff with suspensions of agents under evaluationin the given dosage series. The sprayed plants are allowed to dry andare then inoculated with a suspension of the Phytophthora infestansfungal spores. The plants are maintained at a 60° to 62° F. temperatureand 100% relative humidity for about 40 hours to incubate the spores.The plants are then stored in light at 75° F. for 5 to 6 days at whichtime disease control estimates are made.

Data for the foliar control of rice blast (Piricularia oryzae) on riceplants is demonstrated as follows: Rice plants are trimmed to a heightof approximately 5 inches 24 hours prior to chemical application. Theplants are sprayed to runoff with the chemical agent, allowed to dry andthen inoculated with Piricularia oryzae and maintained in a humidenvironment (75°-85° F) for 24 hours. The plants are then maintained ina greenhouse environment for 7-8 days after inoculation at which timedisease control estimates are made.

The foliar control of grape downy mildew (Plasmopora viticola) on grapeseedlings is demonstrated by the following test. The grape seedlings aresprayed to runoff with suspensions of agents under evaluation in thegiven dosage series. The sprayed plants are allowed to dry and are theninoculated with a suspension of the Plasmopora viticola fungal spores.The inoculated plants are incubated in a humid environment at 65°-70° Ffor 48 hours then stored in light at 75° F for 7 days. The plants arethen evaluated for fungal growth.

The salts of this invention are effective against barley net blotch(Helminthosporium teres) on barley plants. In this test barley plantsare trimmed to a height of approximately 2.5 inches 24 hours prior tochemical application. The plants are sprayed to runoff with the chemicalagent and allowed to dry. The plants are then inoculated withHelminthosporium teres and incubated in a humid environment at 75°-80° Ffor 24 hours. The plants are then transferred to a greenhouse (70°-75°F) for 6 to 7 days at which time they are evaluated by counting thelesions.

The control of wheat stem rust (Puccinia graminis) is demonstrated bythe following procedure. Seven-day-old wheat plants (var. Monon) aretrimmed to approximately 2.5 inches 24 hours prior to chemicalapplication to provide a uniform plant height and to facilitate uniforminoculation. The plants are sprayed to runoff with the chemical agent,allowed to dry and then are inoculated with Puccinia graminis. Theplants are maintained in a humid environment at about 68° F. and arenever allowed to exceed 85° F. A timer is used to permit 12 hours ofcontinuous darkness followed by a minimum of 3 to 4 hours of light withan intensity of 500 ft. candles. At the end of the light period thefogger is turned off and the plants are allowed to dry prior to beingplaced in a greenhouse environment where they are grown for 2 weeks atwhich time treatment comparisons are made.

The results of these biological test are given below in Table VII. Inthis table salts which exhibited a 70% or greater control of aparticular fungus are indicated by a + sign and those which exhibitedless than 70% control are indicated by a - sign. In this table theresults of the test against the following fungi were presented:

Bot -- broad bean gray mold leaf spot (Botrytis cinerea)

Bpm -- bean powdery mildew (Erysiphe polygoni)

Tlb -- tomato late blight (Phytophtora infestans)

Rb -- rice blast (Piricularia oryzae)

Gdm -- grape downy mildew (Plasmopora viticola)

Bh -- barley net blotch (Helminthosporium teres)

Wsr -- wheat stem rust (Puccinia graminis)

                  TABLE VII                                                       ______________________________________                                        Disease Control Level at 150 ppm                                              Example                                                                       No.      BOT    BPM     TLB  RB   GDM   BH   WSR                              ______________________________________                                        1        -      +       +         +     -                                     2        +      +       +    +    +     +                                     3        +      -       +    +    +     -    +                                4        +      -       +    +    +     -    +                                5        +      -       +    +    +     -    +                                6        +      -       +    +    +     -    +                                7        +      -       +    +    +     +    +                                8        +      -       -    +    +     -    +                                9        +      -       -    +    +     -    +                                10       +      -       +    +    +     -    +                                11       +      -       +    +    +     -    +                                12       +      -       -    +    +     -    +                                13       +      -       +    +    +     -                                     14       +      -       +    +    +     -    +                                15       +      -       -    +    +     -    +                                16       -      -       -    +    +     -    +                                17       +      -       -    +    +     -    -                                18       +      -       +    +    +     -    +                                19       +      +       -    +    +     +    +                                20       +      -       -    +    +     -    +                                21       +      -       -    -    +     -    +                                22       +      -       -    -    +     -    -                                23       +      -       -    -    +     -    -                                24       +      -       -    -    +     -    -                                25       +      -       -    +    +     +    +                                26       +      -       -    +    +     -    +                                27       +      -       -    -    +     +    -                                28       +      -       -    -    +     +    -                                29       +      +       -    -    +     +    -                                30       +      +       -    +    +     -    -                                31       +      -       -    +    +     -    -                                32       +      -       -    -    +     -    -                                33       +      +       -    -    +     +    +                                34       +      -       -    +    +     -    +                                35       +      -       -    +    +     -    +                                36       +      +       -    +    +     -    +                                37       +      -       -    +    -     -    -                                38       -      -       -    +    -     -    +                                39       +      -       -    -    +     -    +                                40       +      -       -    +    +     -    -                                41       -      -       -    +    +     -    +                                42       +      -       -    +    +     -    -                                43       -      -       -    +    +     -    -                                44       -      -       -    -    +     -    +                                45       -      -       -    +    +     -    -                                46       +      -       -    +    +     -    -                                47       +      -       -    +    -     -    -                                48       +      -       -    +    +     -    -                                49       +      -       -    +    +     -    +                                50       +      +       +    +    +     +                                     51       +      -       +    +    +     +                                     52       +      +       +    +    +     -                                     53       +      -       +         +     +    +                                54       +              +         +     +                                     55       +      +       +    +    +     +                                     56       -      -       -    +    -     -    -                                57       +      -       -    -    +     -    -                                58       +      -       -    +    +     +    +                                59       +      -       -    +    -     -    -                                60       +      +       +    +    +     -                                     61       -      -       +    +    +     -    +                                62       +      -       -    +    +     -    -                                64       -      -       -    +    -     -    -                                65       +      -       -    +    -     -    -                                66       -      -       -    +    -     -    -                                67       +      -       -    +    +     -    +                                68       +      +       -    +    +     -    +                                69       -      -       -    +    -     -    -                                70       -      +       -    +    -     -    -                                71       -      +       -    +    -     -    -                                72       -      -       -    +    -     -    -                                73       +      -       -    +    -     -    -                                74       -      -       -    +    -     -    -                                75       -      -       -    +    -     -    -                                76       -      -       -    +    -     -    -                                77       -      -       -    +    -     -    +                                78       -      +       -    +    -     -    -                                79       -      -       +    +    +     -    +                                80       -      -       -    +    -     -    -                                81       -      -       -    +    -     -    -                                82       +      -       -    +    +     -    +                                83       +      +       -    +    +     -    +                                84       +      -       +    +    +     +    +                                85       +              +         +     -                                     *86      +      +       +         +     +    +                                ______________________________________                                         *at 300 ppm                                                              

The metal salts of mixed dithiocarbamic acids of this invention areuseful as agricultural fungicides and as such may be applied to variousloci such as the seed, the soil or the foliage. For such purposes thesemetal salts may be used in the technical or pure form as prepared, assolutions or as formulations. The metal salts are usually taken up in acarrier or are formulated so as to render them suitable for subsequentdissemination as fungicides. For example, these metal salts may beformulated as wettable powders, emulsifiable concentrates, dusts,granular formulations, aerosols, or flowable emulsion concentrates. Insuch formulations, the salts are extended with a liquid or solid carrierand, when desired suitable surfactants are incorporated.

It is usually desirable, particularly in the case of foliar sprayformulations, to include adjuvants, such as wetting agents, spreadingagents, dispersing agents, stickers, adhesives and the like inaccordance with agricultural practices. Such adjuvants commonly used inthe art may be found in the John W. McCutcheon, Inc. publication"Detergents and Emulsifier, Annual."

Wettable powders suitable for spraying, can be prepared by admixing thecompound with a finely divided solid, such as clays, inorganic silicatesand carbonates, and silicas and incorporating wetting agents, stickingagents, and/or dispersing agents in such mixtures. The concentration ofactive ingredients in such formulations is usually in the range of 20%to 98%, preferably 40% to 75%. A typical wettable powder is made byblending 50 parts of tetramethylammonium zincethylene-bis-dithiocarbamic acid-dimethyldithiocarbamic acid, 45 partsof a synthetic precipitated hydrated silicon dioxide sold under thetrademark Hi-Sil®, and 5 parts of sodium lignosulfonate (Marasperse®N-22). In another preparation a kaolin type (Barden) clay is used inplace of the Hi-Sil in the above wettable powder, and in another suchpreparation 25% of the Hi-Sil is replaced with a synthetic sodium silicoaluminate sold under the trademark Zeolex® 7.

Dusts are prepared by mixing the metal salt with finely divided inertsolids which can be organic or inorganic in nature. Materials useful forthis purpose include botanical flours, silicas, silicates, carbonatesand clays. One convenient method of preparing a dust is to dilute awettable powder with a finely divided carrier. Dust concentratescontaining 20% to 80% of the active ingredient are commonly made and aresubsequently diluted to 1% to 10% use concentration.

The metal salts can be applied as fungicidal sprays by methods commonlyemployed, such as conventional high gallonage hydraulic sprays, lowgallonage sprays, airblast spray, aerial sprays and dusts. The dilutionand rate of application will depend upon the type of equipment employed,the method of application and diseases to be controlled, but theeffective amount is usually 0.1 lb. to 25 lbs. per acre of the activeingredient.

As a seed protectant, the amount of toxicant coated on the seed isusually at a dosage rate of about 0.1 to 20 ounces per hundred pounds orseed. As a soil fungicide the chemical may be incorporated in the soilor applied to the surface usually at a rate of 0.1 to 25 lbs. per acre.As a foliar fungicide, the toxicant is usually applied to growing plantsat a rate of 0.25 to 10 pounds per acre.

Fungicides which may be combined with the fungicides of this inventioninclude:

(a) Nitrophenol derivatives such as:

dinitro-(1-methylheptyl)phenyl crotonate (dinocap),2-sec-butyl-4,6-dinitrophenyl 3,3-dimethyl acrylate (binapacryl), and2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

(b) heterocyclic structures such as:

N-trichloromethylthiotetrahydro-phthalimide (captan),N-trichloromethylthiophthalimide (folpet), 2-heptadecyl-2-imidazolineacetate (glyodin) 2-octylisothiazolone-3,2,4-dichloro-6-(o-chloroanilino)-s-triazine, diethylphthalimidophosphorothioate, 4-butyl-1,2,4-triazole,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,5-ethoxy-3-trichloromethyl-1,2,4-thiadizole,2,3-dicyano-1,4-dithiaanthraquinone (dithianon),2-thio-1,3-dithio-[4,5-b]quinoxaline (thioquinox). methyl1-(butylcarbamoyl)-2-benzimidazole carbamate (benomyl),2-(4-thiazolyl)benzimidazole,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,pyridine-2-thiol-1-oxide, 8-hydroxyquinoline sulfate.2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,α-(phenyl)-α-(2,4-dichlorophenyl)-5-pyrimidinylmethanol (triarimol),cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide,3[2-(3,5-dimethyl-2-oxycyclohexyl-2-hydroxy]glutarimide (cycloheximide),and dehydroacetic acid;

(c) Miscellaneous halogenated fungicides such as:

tetrachloro-p-benzoquinone (chloranil),1,4-dichloro-2,5-dimethoxybenzene(chloroneb),2,3-dichloro-1,4-naphthoquinone (dichlone), 3,5,6-trichloro-o-anisicacid (tricamba), 2,4,5,6-tetrachloroisophthalonitrile,2,6-dichloro-4-nitroaniline (DCNA), 2-chloro-1-nitropropane,polychloronitrobenzenes such as: pentachloronitrobenzene (PCNB) andtetrafluorodichloroacetone;

(d) Fungicidal antibiotics such as:

griseofulvin, kasugamycin and streptomycin;

(e) Copper-based fungicides such as:

cuprous oxide, basic cupric chloride, basic copper carbonate, coppernaphthenate, and bordeaux mixture; and

(f) Miscellaneous fungicides such as:

diphenyl, dodecylguanidine acetate (dodine), phenylmercuic acetate,N-ethylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide,phenylmercuric monoethanolammonium lactate, p-dimethylaminobenzenediazosodium sulfonate, methyl isothiocyanate, 1-thiocyano-2,4-dinitrobenzene,1-phenylthiosemicarbazide, nickel-containing compounds, calciumcyanamide, lime sulfur, sulfur, and1,2-bis(3-methoxycarbonyl-2-thioureido(benzene (thiophanatemethyl)

The complex metal salts of mixed dithiocarbamic acids of this inventioncan be advantageously employed in various ways. Since these complexespossess broad spectrum fungicidal activity they can be employed in thestorage of cereal grain. These complexes can also be employed asfungicides in turf and orchard applications. Other applications of thecomplexes of this invention such as use on various food crops and theirhabitat will suggest themselves to those skilled in the art ofagriculture and horticulture.

We claim:
 1. A metal salt of the formula: ##STR22## wherein M is a metalcation selected from groups IIA, IIIA, IVA, IB, IIB, VIB, VIIB and VIIIof the Periodic Table; Y is the group ##STR23## where R¹, R², R³ and R⁴are independently hydrogen; (C₁ -C₂₀) unsubstituted alkyl; unsubstitutedphenyl naphthyl, benzyl or phenethyl; phenyl, naphthyl, benzyl orphenethyl substituted with up to three substituents selected from thegroup consisting of methyl, ethyl, methoxy, ethoxy, fluoro, chloro,bromo, iodo, nitro or trihalomethyl; (C₁ -C₂₀) hydroxyalkyl; or (C₁-C₂₀) haloalkyl; a, b, x and y are integers; 2a + b = 2x + y;A is aphenylene or an alkylene chain of 2 to 6 carbon atoms which may bebranched or straight chained; and R is hydrogen or (C₁ -C₄) alkyl.
 2. Ametal salt according to claim 1 wherein M is a metal cation selectedfrom the group consisting of Mg, Ca, Ba, Al, Pb, Cu, Zn, Cd, Cr, Mn, Fe,Co and Ni or combinations thereof.
 3. A metal salt according to claim 2wherein A is an alkylene chain of 2 to 6 carbon atoms.
 4. A method forcontrolling phytopathogenic fungi which comprises applying afungicidally effective amount of a salt according to claim 1 to a plant,to plant seeds or to the plant habitat.
 5. A method according to claim 4wherein the salt is applied to the plant, the plant seeds or the planthabitat at a rate of 0.1 to 25 lbs. per acre.
 6. A fungicidalcomposition which comprises an agronomically acceptable carrier and asthe active ingredient, a salt as set forth in claim
 1. 7. A process forthe preparation of a fungicide which comprises:mixing aqueous oralcoholic solutions of an alkali metal salt of one mole of analkylene-bis-dithiocarbamate of the formula: ##STR24## wherein A isphenylene or (C₂ -C₆) alkylene; about 0.1 to 10 moles of an alkali metalsalt of an alkyl or dialkyldithiocarbamate of the formula: ##STR25##wherein R is independently selected from the group consisting ofhydrogen and (C₁ -C₄) alkyl; about 0.1 to 6.0 moles of an ammonium orphosphonium salt the cation of which has the formula: ##STR26## whereinR¹, R², R³ and R⁴ are independently hydrogen; (C₁ -C₂₀) unsubstitutedalkyl; unsubstituted phenyl, naphthyl, benzyl or phenethyl; phenyl,naphthyl, benzyl or phenethyl substituted with up to three substituentsselected from the group consisting of methyl, ethyl, methoxy, ethoxy,fluoro, chloro, bromo, iodo, nitro or trihalomethyl; (C₁ -C₂₀)hydroxyalkyl; or (C₁ -C₂₀) haloalkyl; then adding to this mixture anaqueous or alcoholic solution of about 0.75 to about 6.0 moles of apolyvalent metal salt.
 8. A process according to claim 7 wherein thereaction is carried out at temperatures from about 20° C. to about 80°C.
 9. A process according to claim 8 wherein the resultant precipitateis filtered and dried at about 40° C. to a constant weight.
 10. Aprocess according to claim 9 wherein a solution of compounds of Formula(I) and a solution of compounds of Formula (II) are added simultaneouslywith a solution of polyvalent metal salt to a solution of a group ofFormula (IV or (V).
 11. A process according to claim 10 wherein A is (C₂-C₆) alkylene and R¹, R², R³ and R⁴ are independently hydrogen, (C₁-C₁₀) unsubstituted alkyl, (C₁ -C₁₀) hydroxyalkyl, or unsubstitutedphenyl, benzyl or phenethyl.
 12. A process according to claim 10 wherein1.0 mole of the sodium salt of ethylene-bis-dithiocarbamate; about 2moles sodium of dimethyldithiocarbamate; about 4 moles of trimethyl(2-hydroxyethyl) ammonium chloride and about 2 moles of zinc chlorideare reacted at temperatures from about 25° C. to about 40° C. in anaqueous solvent.
 13. A metal salt of the formula: ##STR27## wherein M isa metal cation selected from the group consisting of Mg, Ca, Ba, Al, Pb,Cu, Zn, Cd, Cr, Mn, Fe, Co, and Ni, or combinations thereof; Y is thegroup ##STR28## wherein R¹, R², R³, and R⁴ are independently selectedfrom the group consisting of hydrogen, (C₁ -C₁₀) unsubstituted alkyl,(C₁ -C₁₀) hydroxyalkyl, and unsubstituted phenyl, benzyl or phenethyl;a, b, x and y are integers; 2a + b = 2x + y; A is an alkylene chain of 2to 6 carbon atoms; and R is hydrogen or (C₁ -C₄) alkyl.